Aromatic polyether chlorides



Patented Nov. 2, 1937 UNITED STATES AROMATIC POLYETHEB, CHLORIDES HermanA. Brnson, Philadelphia, Pa asslgnor to Riihm & Haas Company,Philadelphia, Pat.

No Drawing. Application my 14, 1936,

' Serial No. 19,118

16 Gianna (Cl. 280-150) This invention relates to condensation prodnetsof monohydric phenols or naphthols withp-chloroethyl-p'-chloroethoxyethyl ether,

Cl-CH2CHzOCHaCHa-OCH2-CH2CI, said condensation products being aromaticpolyether chlorides having the formula R-OCH2--CH2OCHa-.

. CHa-O-CHa-CHaCl wherein R is an aromatic radical of the benzene ornaphthalene series.

It is an object of this invention to provide compounds of the typedescribed which are useful as intermediates in the preparation ofdetergents,

emulsifying and insecticidal agents. I

These products may be prepared in general by heating thep-chloroethyl-p'-chloroethoxyethyl other with the desired phenoliccompound in the presence of an oxide or hydroxide of a metal capable offorming a phenolate with the phenol.

'These metals are preferably those of the first and second groups of theperiodic table, such as sodium, potassium, calcium, magnesium, zinc,etc. In order to prevent the formation of unde- Jsired by-products andto secure as high a yield as possible of the product it is preferable toemploy an excess of the dichloro polyether and an amount of metal oxideor hydroxide approximately equivalent to the amount of the phenoliccompound. The reaction is advantageously carried out in the presence ofwater although inert organic solvents such as alcohol, dioxane, toluene,butanol, etc. may be used either alone or in conjunction with water.

The reaction is applicable to phenols and or 86 pnaphthols containingonly one free phenolic CHI prevent .the formation of halogenfreearomatic others, it is preferable tocarry out" the condensation withfrom 3 to 4 mols of the p-chloroethyl-p-chloroethoxyethyl ether per mol.of the phenol or naphthol used, and to employfrom 1 to 1.2 mols ofcaustic alkali. Thecondensation is usually complete after heating themixture for about 8 hours at 110-115 C. under reflux, while stirringconstantly. The product can be isolated by removing the metal chlorideformed 'in the reaction and distilling the liquid mixture. In

this manner, substantially all of the excess 5-chioroethyl-p-chl0roethoxyethyl ether may be recovered and the desiredproduct isolated by distillation under reduced pressure.

Thefl-aryloxyethyl-p'-chloroethoxyethyl ethers obtained, especially thenuclear alkylated derivatives having 4 to 16 carbon atoms in the .alhlgroup, are useful intermediates for preparing water-soluble sulfonateshaving capillaryactive properties, by condensation with sodium "sulflte.They are readily converted into amine Example 1 CHI 40 hydroxyl. groupbut which may contain one or more relatively inert nuclear substituentssuch as saturated or unsaturated aliphatic, cyclo-alkyl, and arylhydrocarbon radicals, alkoxy, aryloxy, aralkyl, acyi, and nitro groupsor halogen atoms.

Among the typical phenolic compounds which may be used are thefollowing: phenol, 0-, m-,

p-cresol, thymoi, carvacrol, 1,3,5-xylenol, any of the straight-chain orbranched-chain butyl, amyi,

hexyl, heptyl, octyl, decyl, dodecyl, hexadecylphenols, or thecorresponding cresols or xylenols, the o-, m-, or p-phenyl-phenols,benzylphenols, cyclohexylphenols, chlorophenois, or chlorocresols,guaiacol, the o-, m-, or p-benzoylphenols,

nitrophenols, and the correspondingly substituted alpha orbeta-naphthols. I

In order to obtain high yields of the desired 50aryloxy-ethyl-chloroethoxy-ethyl ether, and to C./3 mm. Yield, 83%of-theory.

distilled first, followed by the desired product,

which was a colorless oil boiling at 200-205 Example 2 o-cm-oni-o-oHr-CHr-O-CHr-CHiCl A mixture consisting of 42.5 grams paraphenylphenol,11.7 grams sodium lwdroxide, 15 cc. water, and 187 grams-p-chloroethyl-p'- chloroethoxyethyl ether was heated for 7 hours at 112C. while stirring constantly under reflux. The reaction mixture waswashed with warm water and fractionated in vacuo. The13-pphenyl-phenoxyethyl-B'-chloroethoxyethyl ether p (p naphthoxyethyl)p'- chloroethoxyethyl ether is a colorless oil boiling at 207-212 C./3mm. Yield, 83% of theory.

P. 250-260 C43 mm,

o distilled at 222-229 c. 3 mm. as a colorless oil, Erample 4 Colin-3-OCH|-CH;OCH,CH,OCH -CILCl which quickly solidified to a crystallinemass, A mixture consisting of 44 grams p-cyclohexyl- 10 which, afterrecrystallization from ligroin, melted phenol, 11.7 grams sodiumhydroxide, 15 cc.

at 58 C. Yield, 75% of theory. water, and 187 gramsp-chloroethyl-W-chloro- Example 3 ethoxyethyl ether was heated at110-115 C. for

' 7 hours while stirring constantly under reflux. 15 "(Pom-HFO CH="CHIOCHICHC1 After removal of the water, sodium chloride and excess dichloroether, the residual product was an oil which distilled at 198-200 C./3mm. Yield, A mixture consisting of 38 grams p-naphthol, 56 11.7 gramssodium hydroxide, 15 cc. water, and The flowing tablelglves the730111118 Points 01 so 180. grams chloroethyl p chloroethoxyethyl thefi- -fi whiewethoxyethyl ethers ether was heated at 5 C" Whilev u -mobtained from the phenols shown by condensaconstantly, under reflux. Thesodium chloride tion with fi- -fi' t oxyethy1 and water were removed andthe product frgcether in accordance with this invention. The tionated invacuo. yields varied from 75% to 90% of theory.

B. o -(]H, CH,OCH OHaOCHaCHaCl obtained Phenol used Rls Physicalproperties O Colorless oil Phenol B. P. 148-151" on m.

CH: L Colorless oil p-Ter-butylphenol... CH:- B. P. Eli-168 0.]3 mm.

cm 40 i Colorless oil p-Ter-amylphonol--. GE's-0 B. P. 189-191 0.14 mm,

Yellow oil p-Nitro-pheno] O NO B. P. 213-2l5 0.12 mm,

- Colorless oil .o-Benzylphonol CoHa-Cih-O B. P. mang 0.13 mm. I QColorlm oil O-Cblorphenol Q B. amt-171 0.;3 mm, l

Colorless oil o-Methoryphonoi.... 6 -170 043 mm.

o 61) gen Colorless oil Thymol B. P- 171-174 C./3 mm.

. EEO Colorless oil p-Cresal C B. P. lee-171 C./3 65 l Colorlew oil2,4-Dlohlor l1onol.... 0Q 3.1. l88-193 C./4mln. Cl

Colorlem oil p-Benzylphenol.. CsHr-CH B. P. 241-247 0.14 mm.

p-Benzoylphsnoi..... c.l;-noogolorloss oil I claim: 1. An aromaticpolyether chloride having the formula R 0 c 1, cH,-o cracH,-0-cH,-cmc1in which R is an aromatic radical obtainable from a monohydric phenol. g2. An aromatic polyether chloride having the formulaR-OCHECH,O+CHZCHZOCHT.CHZCI in which R is an aromatic hydrocarbonradical. 3. An aromatic polyether chloride having the formula in which Ris a phenyl radical containing as a nuclear substituent a monovalenthydrocarbon group.

4. An aromatic polyether chloride having the formulaROCH;-CH;-OCH,CH=-O-CH,CH,C1 in which R is a phenyl radical containingas a nuclear substituent an alkyl group.

5. An aromatic polyether chloride having the formula where X is atertiary albl group.

6. The aromatic polyether chloride having the formula CHr-(EOO-CH-CWHPCWMK CI '1. The aromatic polyether chloride having the formula inwhich R. is a phenyl radical containing as a nuclear substituent analkyl group, which comprises heating one mol. of a monohydric phenol,ROhI, with more than one mol. of p-chloroethylp'-chloroethoxyethyl etherin the presence of an oxide or hydroxide of a metal chosen from Groups Iand 11 of the periodic table.

13. The process of preparing an aromatic polyether chloride havingth'eformula where X is a tertiary alkyl group, which comprises heating onemoi. of p-tertiary alkyl phenol with more than one mol. ofp-chloroethyl-p'- chloroethoxyethyl ether in the presence of sodiumhydroxide.

14. The process for preparing the aromat polyether chloride having theformula om-i-Oo-onronro-onrom-o-om-omci Hi 8. The aromatic polyetherchloride having the formula a 9. The process for preparing aromaticpolyether chlorides having the formula in which R is an aromaticradical, which com prises heating one moi. of a monohydric phenol, ROH,with more than one moi. of ,s-chloroethylp'-chloroethoxyethyl ether inthe presence of an oxide or hydroxide of a metal chosen from Groups Iand II of the periodic table. l

10. The process for preparing aromatic polyether chlorides having theformula R o oH2 cH,0- CH,-(:H,0 cm-Cmc1 in which R. is an aromatichydrocarbon radical, which comprises heating one moi. of a monohydricphenol, ROH, with more than one mol. ofp-chloroethyl-p'-chloroethoxyethyl ether in the presence of an oxide orhydroxide of 'a metal which comprises heating one mol. ofp-ter-butylphenol with more than one moi. of p-chloroethyi-p'-chloroethoxyethyi ether in the of sodium hydroxide.

15. The process for'preparing the aromatic polyetherchloride having theformula which comprises heating ohe mol. of p-teramylphenol with morethan one mol. of p-chloroethyl-p'-chloroethoxyethyl ether in thepresence of sodium hydroxide.

16. The process for preparing the aromatic polyether chloride having theformula which comprises heating one moi. of D-cpflfltetramethylbutylphenol with more than one moi. of p-chloroethyl-fl'-chloroethoxyethylether in the presence of sodium hydroxide.

HERMAN A. BRUSON.

